EP2945735A1 - Non-pgm catalysts for orr based on charge transfer organic complexes - Google Patents
Non-pgm catalysts for orr based on charge transfer organic complexesInfo
- Publication number
- EP2945735A1 EP2945735A1 EP14740852.0A EP14740852A EP2945735A1 EP 2945735 A1 EP2945735 A1 EP 2945735A1 EP 14740852 A EP14740852 A EP 14740852A EP 2945735 A1 EP2945735 A1 EP 2945735A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- charge transfer
- transfer salt
- catalytic material
- precursor
- catalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000012546 transfer Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title description 55
- 239000000463 material Substances 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 229920000557 Nafion® Polymers 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- UKHWDRMMMYWSFL-UHFFFAOYSA-N Nicarbazin Chemical group CC=1C=C(C)NC(=O)N=1.C1=CC([N+](=O)[O-])=CC=C1NC(=O)NC1=CC=C([N+]([O-])=O)C=C1 UKHWDRMMMYWSFL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 229940073485 nicarbazin Drugs 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical group [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 3
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000000133 mechanosynthesis reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 238000010438 heat treatment Methods 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000010411 electrocatalyst Substances 0.000 description 18
- 239000000446 fuel Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000013459 approach Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910002848 Pt–Ru Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002198 insoluble material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- 229910002558 Fe-Nx Inorganic materials 0.000 description 1
- 241000725579 Feline coronavirus Species 0.000 description 1
- 229910002559 Fe−Nx Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KWUQLGUXYUKOKE-UHFFFAOYSA-N propan-2-ol;tantalum Chemical compound [Ta].CC(C)O.CC(C)O.CC(C)O.CC(C)O.CC(C)O KWUQLGUXYUKOKE-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Fuel cells are receiving increasing attention as a viable energy-alternative. In general, fuel cells convert electrochemical energy into electrical energy in an environmentally clean and efficient manner. Fuel cells are contemplated as potential energy sources for everything from small electronics to cars and homes. In order to meet different energy requirements, there are a number of different types of fuel cells in existence today, each with varying chemistries, requirements, and uses.
- Direct Methanol Fuel Cells rely upon the oxidation of methanol on an electrocatalyst layer to form carbon dioxide. Water is consumed at the anode and produced at the cathode. Positive ions (H+) are transported across a proton exchange membrane to the cathode where they react with oxygen to produce water. Electrons can then be transported via an external circuit from anode to cathode providing power to external sources.
- DMFCs Direct Methanol Fuel Cells
- PEM fuel cells also called proton exchange membrane fuel cells
- PEM fuel cells use pure hydrogen (typically supplied by a hydrogen tank) as a fuel.
- a stream of hydrogen is delivered to the anode side of a membrane-electrode assembly (MEA), where it is catalytically split into protons and electrons.
- MEA membrane-electrode assembly
- the positive ions are transported across a proton exchange membrane to the cathode where they react with oxygen to produce water.
- M-N-C Metal-Nitrogen-Carbon
- MEAs fuel cell membrane electrode assemblies
- Critical aspects of the materials include the presence of metallic particles, conjugated carbon-nitrogen-oxide-metallic networks, and nitrogen-bonded carbon.
- the metallic phase includes metallic, oxide, carbide, nitride, and mixtures of these states.
- the chemical states and bonding of the N/C/M networks and N/C networks influences performance, for example, increased overall nitrogen content improves ORR performance.
- these systems still suffer from several significant drawbacks including: low stability in acidic environments, low durability in acid and alkaline environments, high costs of nitrogen precursors and low activity in ORR compared with platinum.
- the present disclosure provides novel materials and methods for making the same.
- the present disclosure provides a method of preparation of novel non-platinum group metal (PGM) catalytic materials utilizing a sacrificial support- based approach and using inexpensive and readily available precursors including precursors of transition metals and charge transfer salts enriched with nitrogen that is useful in different applications including fuel cells.
- PGM platinum group metal
- the present dislcosure provides a method of preparation of novel non-platinum group metal materials utilizing a mechanosynthesis-based approach.
- the present disclosure provides a method of preparation of novel non-platinum group metal materials utilizing a combination of the mechanosynthesis and sacrificial support-based approaches.
- the present disclosure provides novel non- platinum group metal catalytic materials formed from the methods above.
- Fig. 1 is an SEM image of an Fe-NCB catalyst produced using the methods described herein.
- Fig. 2 is a TEM image of the Fe-NCB catalyst of Fig. 1.
- Fig. 3 is a high resolution TEM image of the Fe-NCB catalyst of Figs. 1 and 2.
- Fig. 4 shows that RRDE data (ring current- top and disk current-bottom) of catalysts produced usign the methods described herein with various heat treatment protocols.
- Fig. 5 shows RDE measurements of the durability of a catalyst produced using the methods described herein measured with a DOE Durability Working Group (DWG) proposed protocol.
- DWG DOE Durability Working Group
- Fig. 6 shows RDE measurements of the durability of the catalyst produced using the methods described herein measured with a load eyeing protocol.
- Fig. 7 shows MEA performance data of the Fe-NCB catalyst prepared using the methods described herein with varying Nafion content under the recommended DOE conditions of H2/O2 operation, 100 RH, and 1 bar O2 partial pressure (1.5 bar total pressure or 0.5 barg backpressure).
- Fig. 8 shows kinetic current density of the Fe-NCB catalyst prepared using the methods described herein with varying Nafion content under the recommended DOE conditions of H2/O2 operation, 100 RH, and 1 bar O2 partial pressure (1.5 bar total pressure or 0.5 barg backpressure).
- the present disclosure provides novel materials and methods for making the same.
- the present disclosure provides novel catalysts and catalytic materials and methods for making the same.
- the present disclosure provides a sacrificial support- based method, a mechanosynthesis-based method, and a combined sacrificial support/mechanosynthesis support based method that enables the production of supported or unsupported catalytic materials and/or the synthesis of catalytic materials from both soluble and insoluble materials.
- the methods disclosed herein can be used to produce catalytic materials having a well-defined morphology, and in particular, a well-defined porous morphology, the catalytic materials described herein can be tailored to meet application- specific needs in terms of size, shape, and activity.
- catalyst is used to refer to a final product, suitable for use, for example, in a fuel cell, which has catalytic activity.
- the catalyst may include multiple types of materials, some of which may not in themselves have catalytic activity (for example, supporting material.)
- catalytic material is any material which has catalytic activity either on its own or as part of a catalyst.
- a catalytic material according to the present disclosure may be synthesized utilizing a sacrificial support-based method.
- the term "sacrificial support” is intended to mean a material which is used during the synthesis process to provide a temporary structural support, but which is mostly or entirely removed during the synthesis step.
- a sacrificial support is infused M-N-C precursors wherein the metal is provided by one or more transition metal precursors and the nitrogen and carbon are provided by one or more charge transfer salt precursors.
- the transition metal may be iron.
- Suitable iron precursors include, but are not limited to, iron nitrate, iron sulfate, iron acetate, iron chloride, etc.
- other transition metals such as Ce, Cr, Cu Mo, Ni, Ru, Ta, Ti, V, W, and Zr can be substituted in place of iron, by simply using precursors of those metals instead.
- Examplary transition metal precursors include, but are not limited to cerium nitrate, chromium nitrate, copper nitrate, ammonium molybdate, nickel nitrate, ruthenium chloride, tantalum isopropoxide, titanium ethoxide, vanadium sulfate, ammonium tungtanate and zirconium nitrate.
- the presently described methodologies may utilize precursors of two or more metals to produce multi-metallic catalysts.
- charge transfer salts are defined as an association of two or more molecules or atoms, or of different parts of one large molecule, in which a fraction of an electronic charge is transferred between the molecular or atomic entities.
- the charge transfer salt maybe a nitrogen enriched charge transfer salt such as nicarbazin.
- suitable charge transfer salts include, but are not limited to tetracyanoquinodimethane, tetrathiafulvalene, and multiferroics.
- the term "precursor” is used to refer to a compound which participates in a chemical reaction by contributing one or more atoms to a compound that is formed as the product of the chemical reaction or otherwise contributes to the formation of the product. For example in generating a gaseous product that creates a small pore or void in the final product or in helping create the chemical structure of the final product as in the case of nickel nanoparticles leading to the growth of carbon fibers.
- the sacrificial support may be synthesized and infused in a single synthesis step or the sacrificial support may be synthesized first (or otherwise obtained) and then infused with the charge transfer salt precursor(s) and the appropriate/desired transition metal precursor(s).
- the infused sacrificial support is then subjected to heat treatment, (such as pyrolysis) in an inert (N 2 , Ar, He, etc.) or reactive (NH 3 , acetonitrile, etc.) atmosphere.
- sacrificial support which is non-reactive to the catalytic materials under the specific synthesis conditions used. Accordingly, it will be appreciated that silica is a preferred material for the sacrificial support, but that other suitable materials may be used.
- suitable sacrificial supports include, but are not limited to zeolites, aluminas, and other metal oxides, sulfides, nitrides, or mixtures.
- the support may take the form of spheres, particles, or other two or three dimensional regular, irregular, or amorphous shapes.
- the spheres, particles, or other shapes may be monodisperse, or irregularly sized.
- the spheres, particles, or other shapes may or may not have pores and such pores may be of the same or different sizes and shapes.
- the size and shape of the silica particles may be selected according to the desired shape(s) and size(s) of the voids within the electrocatalyst material. Accordingly, by selecting the particular size and shape of silica particles, one can produce an electrocatalyst having voids of a predictable size and shape. For example, if the silica particles are spheres, the electrocatalyst will contain a plurality of spherical voids. Those of skill in the art will be familiar with the electrocatalyst Pt-Ru black, which consists of a plurality of platinum-ruthenium alloy spheres.
- An electrocatalyst formed from using silica spheres with the above-described method looks like a negative image of the Pt-Ru black; the space that existed as a void in the Pt-Ru black is filled with metal electrocatalyst, and the space that existed as metal electrocatalyst in the Pt-Ru black is void.
- silica spheres of any diameter may be used.
- silica particles having a characteristic length of between 1 nm and 100 nm in more preferred embodiments, silica particles having characteristic lengths of between 100 nm and 1000 nm may be used and in other preferred embodiments, silica particles having characteristic lengths of between 1 mm and 10 mm may be used.
- Further mesoporous silica can also be used in the templating synthesis approach. In this case the templating involves intercalating the mesopores of the material and results in a self-supported electrocatalysts with porosity in the 2-20 nm range.
- the silica template is Cab-O-Sil amorphous fumed silica (325 m 2 /g).
- the spheres serve as the template for the formation of the electrocatalyst, in an embodiment where silica particles having an average diameter of 20 nm is used, the spherical voids in the electrocatalyst will typically have a diameter of approximately 20 nm.
- silica particles that are commercially available, and such particles may be used.
- known methods of forming silica particles may be employed in order to obtain particles of the desired shape and/or size.
- the material is heat treated either in an inert atmosphere such as N 2 , Ar, or He, or in a reactive atmosphere such as N3 ⁇ 4 or acetonitrile.
- inert atmospheres are typically used when the infused materials are nitrogen rich, as the inert atmosphere enables the production of a high number of active sites with Fe (or other metal) N4 centers.
- the materials of the present are subjected to heat treatment in a reactive atmosphere.
- optimal temperatures for heat treatment are typically between 500°C and 1100°C.
- heat treatment may preferably be between 800°C and 1000°C, or more preferably between 875°C and 925°C.
- heat treatment of around 900°C is preferred, as our experimental data showed that materials heat treated at this temperature for 1 hour produced catalysts having a high amount of catalytic activity for certain specific materials (see experimental section below).
- the sacrificial support is removed resulting in a porous, unsupported catalytic material.
- the porous, nonsupported catalytic material consists only of materials derived from the initial precursor materials.
- Removal of the sacrificial support may be achieved using any suitable means.
- the sacrificial support may be removed via chemical or thermal etching.
- suitable etchants include NaOH, KOH, and HF.
- KOH it may be preferable to use KOH, as it preserves all metal and metal oxide in the catalyst and, if the species are catalytically active, use of KOH may, in fact, increase catalytic activity.
- HF may be preferred as it is very aggressive and can be used to remove some poisonous species from the surface of the catalyst. Accordingly, those of skill in the art will be able to select the desired etchants based on the particular requirements of the specific catalytic material being formed.
- the presently described catalytic materials can also be synthesized using a double heat treatment procedure.
- the charge transfer salt and metal precursors are infused in the sacrificial support, which is then subjected to a first heat treatment step, such as pyrolysis in order to produce an intermediate material that is rich with unreacted iron.
- a first heat treatment step such as pyrolysis
- the sacrificial support can be removed after the first heat treatment using chemical etching or other suitable means as described above.
- the intermediate material is then subjected to a second heat treatment step, which may be, for example, a second pyrolysis treatment, resulting in newly formed active sites.
- This second heat treatment step can also be useful for removing any volatile species (such as HF) that may have been introduced during chemical etching, if performed, can introduce desirable surface defects and can extend the open-pore structure that was original created by the sacrificial support. If the sacrificial support is not removed after the first heat treatment step, it can be removed after the second heat treatment step, again using the methods described above.
- any volatile species such as HF
- the different heat treatment steps may be conducted under different conditions, for example at different temperatures and/or for different durations of time.
- the first heat treatment step may be performed at a higher temperature, such as 800°C for 1 hr and the second heat treatment step may be performed at a temperature between 800 and 1000°C for a period of time between 10 minutes and 1 hour.
- a mono-metallic catalyst may not be sufficiently stable or active to replace traditional platinum- or platinum alloy- based catalysts. Accordingly, as indicated above, according to some embodiments, the presently described method may incorporate the use of precursors of multiple metals in order to achieve a desired stability and/or activity.
- the present disclosure further provides a method for large-scale preparation of the presently described catalysts.
- the present disclosure provides a method which combines a sacrificial support-based methodology with spray pyrolysis to produce self-supported catalysts.
- the spray pyrolysis method is a continuous method while the sacrificial support-based methodology is performed batch-wise.
- the charge transfer salt and metal precursor materials described herein are mixed with a silica support, atomized, and dried in a tube furnace. The powder obtained from this procedure is then collected on a filter. The collected powder is then heat treated. Finally, the sacrificial support is removed, for example by leaching with HF or KOH.
- the present disclosure provides a method for forming non-PGM catalytic materials utilizing a mechanosynthesis based approach.
- the herein described mechanosynthesis-based approach enables, for example, the preparation of a variety of materials including, but not limited to, catalytic materials formed from insoluble materials.
- the method employs ball-milling and may or may not utilize a support, which may or may not be sacrificial.
- solvents may be used, if desired.
- Ball-milling has been described previously in referenced to M-N-C catalyst material synthesis as a method for filling the pores of a carbon support with a pore-filler. See e.g., Jaouen et al. [44]. However, in the methods described in the present disclosure, ball-milling is used to enable mechanosynthesis, alleviating the need for solvent-based preparation methods.
- the term "ball mill” is used to refer to any type of grinder or mill that uses a grinding media such as silica abrasive or edged parts such as burrs to grind materials into fine powders and/or introduce to the system enough energy to start a solid state chemical reaction that leads to the formation of a catalyst.
- the ball mill used should be capable of producing enough energy to initiate the desired chemical reaction or achieve the desired level of mixing.
- a catalytic material according to the present disclosure may be synthesized by ball milling the charge transfer salt and transition metal precursors under sufficient conditions to initiate polymerization of the various precursors, thereby forming (or initating formation of) an M-N-C polymer.
- the M-N-C polymer is then subjected to heat treatment, (such as pyrolysis) in an inert (N 2 , Ar, He, etc.) or reactive (N3 ⁇ 4, acetonitrile, etc.) atmosphere at a sufficient temperature to produce a catalytic material.
- the entire process is performed dry, by which is meant, without the presence of any added solvents.
- all reactants i.e. precursors
- a ball mill in powder form and the entire process is conducted without the addition of any liquids.
- a supporting material which may or may not be sacrificial may also be included.
- a powder is a dry, bulk solid composed of a large number of very fine particles that may flow freely when shaken or tilted. Because the method can be practiced without the presence of any solvents, the method enables the synthesis of catalysts formed from insoluble materials. Examples of insoluble materials which can be used to form catalysts according to the present disclosure include, but are not limited to polyacrylonitrile, melamine, polyurethane etc.
- Exemplary characteristics which may be examined with regard to the selection of nitrogen, carbon, or nitrogen-carbon precursors used for producing catalytic materials as described herein include, but are not limited to: (1) carbon content; (2) nitrogen content; and (3) thermal stability, i.e. the volatility of the molecules and resistance to decomposition due to heating.
- the degree of carbon content is related to the porosity of the final product, where carbon content is inversely related to more open final structure.
- a porous, open-frame matrix will be formed if each molecule of the carbon precursor contains, on average, at least 5 carbon atoms.
- the nitrogen richness of the precursor may need to be taken into account.
- precursors should be chosen which will remain stable under the thermal conditions to be used. For example, if the methodology to be used requires pyrolysis at a temperature of above 700°C (a minimum temperature frequently required for active-site formation), it is important that the precursor remain stable at temperatures above 700°C.
- the M-N-C precursors described herein are ball- milled in the presence of supporting material so as to enable infusion of the M-N-C precursors on, around, and throughout (if the supporting material is porous) the supporting material.
- suitable supporting materials include, but are not limited to carbon blacks, carbon nanotubes, conductive oxides or nitrides such as Indium Tin oxide or Molybdenum Nitride etc. or materials that may not be initially conductive but may be made so after processing, such as T1O2 that can be made conductive after chemical or thermal reduction or oxygen content or post synthesis doping.
- T1O2 that can be made conductive after chemical or thermal reduction or oxygen content or post synthesis doping
- non-PGM catalytic materials may be formed using a method that combines both the ball-milling and sacrificial support-based techniques described above.
- the M-N-C precursors described herein are ball-milled in the presence of a sacrificial support, which is then removed after the pyrolysis as described above, resulting in a porous, non-supported catalytic material.
- the porous, nonsupported catalytic material consists only of materials derived from the initial precursor materials.
- the obtained solid was ground to a fine powder in an agate mortar and then subjected to heat treatment (HT).
- the general conditions of HT were UHP nitrogen (flow rate of 100 cc min-1), 20 deg min-1 temperature ramp rate.
- the experimental variable component of heat-time trajectory were temperatures and duration of HT (900 °C, 1 hour; 950 °C, 30 minutes and 950 °C, 1 hour).
- silica was leached using 25 wt. HF overnight.
- Fig. 1 The SEM image in Fig. 1 shows that the Fe-NCB catalyst has several levels of porosity, which originates from the removal of Si02 nanoparticles as well as morphological defects formed during nicarbazin decomposition.
- TEM Fig. 2 show very transparent open structure with repetitive morphological units.
- High resolution TEM Fig. 3 shows graphitic planes along with amorphous type of carbon.
- EDS analysis confirms the presence of Fe while no observable metal particles in TEM images points towards extremely small homogeneously distributed iron particles throughout the nitrogen enriched carbon network.
- High resolution XPS spectra show that the amounts of nitrogen (4.7 at ) and iron (0.39 at. ) are similar to other M-N-C electrocatalysts.
- the sample has significant amounts of pyridinic nitrogen (398.8 eV) as well as Fe-Nx centers (399.6 eV) which previously have been linked to higher activity of ORR electrocatalysts.
- FIGs. 7 and 8 show the MEA performance of the Fe-NCB catalyst under the recommended DOE conditions of H2/O2 operation, 100%RH, and 1 bar O2 partial pressure (1.5 bar total pressure or 0.5 barg backpressure).
- Three MEAs with the same catalyst loading of 4 mg/cm 2 but different Nafion content were investigated.
- the open circuit voltage (OCV) was 0.92V and did not change with increasing Nafion content.
- Fig. 7 shows that increasing the ionomer content from 35% to 55% significantly changes the iV performance.
- the poor iV performance of the 35wt% Nafion MEA may be attributed to incomplete Nafion coverage of the non-PGM active sites. Better ionomer coverage was achieved upon increasing the Nafion content to 45% and 55% as evidenced by the significant improvement in the iV curve. Increasing the ionomer content from 45% to 55% resulted in further increased kinetic currents. As shown in Fig. 8, the MEA containing the Fe- NCB catalyst with 55% Nafion gave kinetic current of 100 mA cm-2 at 0.8 ViR-free. This is the first report of a fuel cell performance that meets the current DOE design target for non- PGM cathode PEMFC catalysts for potential future automotive applications.
Abstract
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PCT/US2014/011774 WO2014113525A1 (en) | 2013-01-16 | 2014-01-16 | Non-pgm catalysts for orr based on charge transfer organic complexes |
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WO2014085563A1 (en) * | 2012-11-27 | 2014-06-05 | Stc.Unm | Mechanochemical synthesis for preparation of non-pgm electrocatalysts |
US10619256B2 (en) | 2015-02-16 | 2020-04-14 | Stc.Unm | Materials with atomically dispersed chemical moieties |
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US7678728B2 (en) * | 2006-10-16 | 2010-03-16 | Stc.Unm | Self supporting structurally engineered non-platinum electrocatalyst for oxygen reduction in fuel cells |
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US20110287174A1 (en) * | 2008-08-21 | 2011-11-24 | Board Of Trustees Of Michigan State University | Novel catalyst for oxygen reduction reaction in fuel cells |
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US9502719B2 (en) * | 2011-06-15 | 2016-11-22 | Stc.Unm | Cathode catalysts for fuel cell application derived from polymer precursors |
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